Dear Andrei,

I did 2x2x2 supecell block and i get an increased bandgap(1.9 eV) almost
twice to bulk(0.9 eV). I did 4x4x4 , results are much better although still
a bit off.
Although i did not put the supercellblock back into siesta with twice the
parameters(will do it). Now , i really start scratching  my head. I checked
manually bulk cell and it is R point for sure (1/2,1/2,1/2).
Any ideas ?

Thank you.






On Wed, Aug 21, 2013 at 8:18 AM, <[email protected]> wrote:

> OK Andrei.
> Now the chemical formula makes sense.
> (Is the methyl ammonium rotating in its site?
> Disordered in this sense? - Must be funny... - A nice task for Siesta)
>
> 1. The 2x2x2 supercell would nicely map X, M and R points
> of the primitive cell onto its new Gamma. Hopefully it's easy
> to trace "by hand", checking contributions from different atoms
> to the wavefunction at these points in case of difficulty.
> I don't understand why do you need a 3x3x3 supercell if you are
> interested just in folding. Must be a long calculation...
>
> 2. Be careful with the supercell block; my suggestion is
> to use it just for generating the supercell, then put the generated
> coordinates into the input (or start from XV) and deactivate
> the supercell block. Otherwise it is easy to make an error.
>
> Good luck
>
> Andrei Postnikov
>
>
> > Thank you Andrei.
> >
> > 1. I do apologize for the typo. System is pervoskite (CH3NH3)SnI3. It has
> > 12 atoms in cubic cell.
> > 2. Going to supercell should not increase the bandgap. I agree on this.
> > 3. I did tetragonal cell of the same system of 48 atoms , and it looks ok
> > if i  use superecell but it has bandgap  at G-point.
> > 4. I looked structures before, basically 12 atoms at 8x8x8 k-mesh gives
> > bandgap of 0.95 eV, whereas with %blocksupercell 3 3 3 %endblcoksupercell
> > with only G point  gives 1.6 eV.
> > 5. And you are right, i also started to suspect that zone folding is the
> > problem(i mean, my whole point of doing supercell calculations is to map
> > R-point into G-point).
> > 6. Visually it looks ok. It contains methylammonium. The only thing it
> > might have is the dipole moment.
> >
> > Witll try to use 2x2x2,4x4x4 (It should correctly map R point onto G
> > point,
> > correct me if i'm wrong )  supercell to see whether problem disappears.
> >
> >
> > With Best Regards, Andrei Buin.
> >
> >
> >
> > On Wed, Aug 21, 2013 at 6:29 AM, <[email protected]> wrote:
> >
> >> Dear Andrei:
> >> I don't see how your system can be a perovskite,
> >> nor how CH3N3SnI3 sums up to 12 atoms. I'll appreciate if you
> >> give a hint, just for my education.
> >> However, this is beyond the point.
> >> In principle, a mere passing to a supercell
> >> should not result in an increase of the band gap.
> >> The mapping of k-points may be not exact, i.e.,
> >> Gamma of the 3*3*3 supercell maps onto 0, 1/3, 2/3 [*(2*pi/a)]
> >> divisions along axes of the reciprocal cell,
> >> none of which points includes R=(1/2 1/2 1/2). You can check
> >> what the band gap (in the primitive cell) is at (1/3 1/3 1/3),
> >> or at (3/8 3/8 3/8), the closest of your k-points at the 8x8x8 mesh.
> >> [However, you say that you have an automatic k sampling, then
> >> the chances are that your mesh is shifted... and does not contain
> >> the R point..?]
> >> Apart from these tests, I think that some simple error in structure
> >> (as simple as a wrong lattice constant in a supercell, sorry)
> >> is a very good candidate for this kind of problem.
> >> To check it, it might be a good idea to have a view at both structures
> >> (the primitive one and the supercell) as stored in corresponding XV
> >> files,
> >> and to compare their corresponding DOS.
> >>
> >> Again apart from all this, if your system contains methyl azide,
> >> I think it could be tricky to initialize the different charge states
> >> at different N atoms correctly... If you just let it go as it wish
> >> the calculation may converge to something wrong... Even to differently
> >> wrong in two different supercells.
> >>
> >> Sorry for too many suggestions.
> >>
> >> Best regards
> >>
> >> Andrei Postnikov
> >>
> >>
> >> > Dear Siesta users,
> >> >
> >> > I'm having very bizarre problem.
> >> > I'm simulating the primitive cubic unit cell(12 atoms) of the
> >> CH3N3SnI3
> >> > perovksite  with GGA and PBE and gives me band gap of Eg=0.9 eV at R
> >> point
> >> > with 8x8x8 Moshkrof automatic k sampling(i know it's wrong in DFT, but
> >> > still) and then i use supercell approach built  in  with 3x3x3 unit
> >> > cell(432 atoms) with Gamma point only and i get a bangap of 1.6 eV.
> >> I've
> >> > checked against plane cutoff convergence seems ok.  I thought maybe
> >> > dispersion  is too big so one should sample it more finely, but it
> >> turns
> >> > out  meff=0.13me, which should be fine. Any ideas ?
> >> >
> >> >
> >> > With Best Regards, Andrei Buin.
> >> >
> >>
> >>
> >
>
>

Responder a